JP5925879B2 - Disulfide dye - Google Patents

Description

  The present invention relates to novel disulfide dyes, compositions thereof, methods for their preparation, and keratin fibers, wool, leather, silk, cellulose or polyamide, especially keratin-containing fibers, cotton or nylon, and preferably hair, more preferably Relates to its use for dyeing organic materials such as human hair.

  For example, it is known from WO 95/01772 that cationic dyes can be used to dye organic materials such as keratin, silk, cellulose or cellulose derivatives, and also synthetic fibers such as polyamide. Cationic dyes exhibit a very vivid color tone. The disadvantage is its unsatisfactory wash fastness.

  RS Asquith, P. Carthew, and TT Francis in JSDC May 1973, pages 168-172 show that ortho-azodisulfide dyes do not cause covalent bonding with wool keratin fibers and para-azo. It is stated that the disulfide dye caused some covalent bonds with wool only at high concentrations.

WO95 / 01772

JSDC, May 1973, pages 168-172

  The actual technical problem of the present invention was to provide dyes distinguished by deep dyeing that have good fastness properties with respect to washing, light, hair washing and friction.

Thus, the present invention provides the formula
(1) A- (X ₁ ) _p- (C _sat ) _r -SS- (C _sat ) _q- (X ₂ ) _p -D
Or expression

[Where
A is selected from the residues of cationic dyes;
X ₁ and X ₂ are at least one selected from -N (R ₁ )-, N ⁺ (R ₁ ) (R ₂ )-, -O-, -S-, -CO-, -SO _2- . An optionally substituted, saturated or unsaturated, fused or non-fused, aromatic or non-aromatic, optionally intervened by a divalent group and / or optionally containing at least one identical or different heteroatom (heterocyclic) cyclic group families mediated optionally from C ₁ -C ₃₀ hydrocarbon chain, saturated or unsaturated, selected independently of one another,
V is optionally substituted by hydroxy, C ₁ -C ₃ alkylene,
D is a group selected from -N (CO) -R ₃ ;
C _sat and C ′ _sat are, independently of one another, optionally substituted, optionally cyclic, linear or branched C ₁ -C ₁₈ alkylene chains;
R ₁ and R ₂ are independently selected from hydrogen, C ₁ -C ₄ alkyl, hydroxyalkyl, or aminoalkyl;
R ₃ is C ₁ -C ₄ alkyl;
p, q, and r are each independently 0 or 1]
Of the compound.

Preference is given to compounds of the formula (1) or (2),
A is represented by the formula (1a) WN = N-Ar-, (1b) Ar-N = NW-, and (1c) Ar-N (R ₄ ) -N = CH-W-
[Where
W is a fused or non-fused aromatic or non-aromatic heterocycle containing quaternary ammonium;
Ar is optionally at least one halogen atom, at least one alkyl group, at least one hydroxyl group, at least one alkoxy group, at least one hydroxyalkyl group, or at least one amino group or (di) alkylamino group. Selected from substituted C ₅ or C ₆ aryl groups and naphthyl-type aromatic bicycles;
R ₄ is hydrogen or C ₁ -C ₄ alkyl]
It is a compound which is a group.

  Preferably, the residue of the organic dye is selected from azo, azomethine, hydrazomethine, merocyanine, methine, and styryl dyes, and more preferably azo, azomethine dyes, and hydrazomethine dyes.

Suitable nitroaryl dyes according to the invention are for example selected from the following compounds:
4-amino-1-nitrobenzene, 2-amino-6-chloro-4-nitrophenol, 2-amino-3-nitrophenol, 2-amino-1-nitrobenzene, 1,4-diamino-2-nitrobenzene, 4- Acetylamino-1-amino-2-nitrobenzene, 1,2-diamino-4-nitrobenzene, 1-amino-2-methyl-6-nitrobenzene, 3-amino-6-methylamino-2-nitro-pyridine (Azarot) , Picramic acid, 4-amino-3-nitrophenol, 4-amino-2-nitrophenol, 6-nitro-o-toluidine, 1,4-bis- (2-hydroxyethyl) amino-2-nitrobenzene, 1- (2-hydroxyethyl) amino-2-nitro-benzene (HC Yellow No. 2), 1- (2-hydroxyethyl) amino-2- (2-hydroxyethyl) oxy-4-nitro-benzene (HC Yellow No. 4), 1-amino-2- (2-hydroxyethyl) amino-5-nitro-benzene (HC Yellow No. 5), 1- (2,3-dihydroxypropyl) amino-4- Trifluoromethyl-2-nitro-benzene (HC Yellow No. 6), 1- (2-hydroxyethyl) amino-4-chloro-2-nitro-benzene (HC Yellow No. 12), 1-amino-2- Nitro-4- [bis (2-hydroxyethyl)] amino-benzene (HC Red No. 13), 4-chloro-2,5-bis [(2,3-dihydroxypropyl) amino] -1-nitro-benzene (HC Red No. 11), 1-amino-5-chloro-4- (2,3-dihydroxypropyl) amino-benzene (HC Red No. 10), 1-amino-2-nitro-4- (2- Hydroxyethyl) amino-benzene (HC Red No. 7), 2-chloro-5-nitro-N- (2-hydroxyethyl) -1,4-phenylenediamine, 1-[(2-hydroxyethyl) -amino] -2-nitro-4-amino-benzene (HC Red No. 3), 4-amino-2-nitro-diphenylamine (HC Red No. 1), 2-nitro-4'-hydroxy-diphenylamine (HC Orange No. 1), 1-amino-3-methyl-4- (2-hydroxyethyl) amino-6-nitrobenzene (HC Violet No. 1), 2- (2-hydroxyethyl) amino-5- (bis (2-hydroxyethyl)) amino-1-nitro-benzene (HC Blue No. 2), 1- (2-hydroxyethyl) amino -2-Nitro-4-N-ethyl-N- (2-hydroxyethyl) amino-benzene (HC Blue No. 12), 4-amino-3,5-dinitro-benzoic acid, 4-amino-2-nitro Diphenylamine-2'-carbonic acid, 2- (4'-amino-2'-nitroanilino) -benzoic acid, 6-nitro-2,5-diaminopyridine, 2-amino-6-chloro-4-nitrophenol, 4- Amino-4'-nitrostilbene-2,2'-disulfonic acid, 4'-amino-4-nitrodiphenylamine-2-sulfonic acid, 4'-amino-3'-nitrobenzophenone-2-carbonic acid, 1-amino- 4-nitro-2- (2'-nitrobenzylideneamino) -benzene, 2- [2- (diethylamino) ethylamino] -5-nitroaniline, 3-amino-4-hydroxy-5-nitrobenzolesulfonic acid, 3 -Amino-3'-nitrobiphenyl, 3-amino-4-nitro-acenaphthene, 2-amino-1-nitronaphthalene, 5-amino-6-nitrobenzo-1,3-dioxole, 2-amino-6-nitrobenzothiazole, 4- (3-hydroxypropyl Amino-3-nitro-phenol (HC Red BN), 2-amino-4,6-dinitro-phenol, 3-nitro-4- (2-hydroxyethyl) -aminophenol, 2- (2-hydroxyethyl) Amino-4,6-dinitrophenol, 2-amino-6-chloro-4-nitrophenol, 2-chloro-6-ethylamino-4-nitro-phenol, 1- (2-hydroxyethyl) amino-4-methyl 2-nitrobenzene, 1- (2′-ureidoethyl) amino-4-nitrobenzene, 4-amino-2-nitro-diphenylamine-2′-carbonic acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline and 4-ethylamino-3-nitrobenzoic acid.

  Suitable anthraquinone dyes suitable for the process of the invention are the following compounds: 1-[(3-aminopropyl) amino] -anthraquinone (HC Red No. 7), 2-[(2-aminoethyl) Amino] -anthraquinone (HC Orange No. 5), 1,4,5,8-tetraamino-anthraquinone (Disperse Blue 1), 1-[(2-hydroxyethyl) amino] -4-methylamino-anthraquinone (Disperse Blue 3), 1,4-[(2-hydroxyethyl) amino] -5,8-dihydroxy-anthraquinone (Disperse Blue 7), 1,4-diamino-2-methoxy-anthraquinone (Disperse Red 11), 1- Amino-4-hydroxy-anthraquinone (Disperse Red 15), 1,4-diamino-anthraquinone (Disperse Violet 1), 1-amino-4-methylamino-anthraquinone (Disperse Violet 4) and 1-amino-4-isopropylamino -Anthraquinone (Disperse Violet 15).

Suitable azo dyes are, for example, the following compounds:
4-Amino-4 '-[bis (2-hydroxyethyl)] amino-azobenzene (Disperse Black 9), 4-amino-4'-nitro-azobenzene (Disperse Orange 3), 3-hydroxy-4-[(2 -Hydroxy-naphth-1-yl) azo) -7-nitro-naphthalene-1-sulfonic acid-chromium complex (Acid Black 52), 1-amino-2- (3'-nitro-phenylazo) -7-phenylazo- 8-naphthol-3,6-disulfonic acid (Acid blue Nr. 29), 1-amino-2- (2'-hydroxy-4'-nitrophenylazo) -8-naphthol-3,6-disulfonic acid (Palatinchrome) green), 1-amino-2- (3′-chloro-2′-hydroxy-5′-nitrophenylazo) -8-naphthol-3,6-disulfonic acid (Gallion) and diamino-3 ′, 5′- Dinitro-2'-hydroxy-5-methyl-azobenzene (Mordant brown 4).

  Suitable cationic dyes are the following compounds: N- [4-[[4- (Diethylamino) phenyl] [4- (ethylamino) -naphth-1-yl] methylene] -2,5-cyclohexadien-1-ylidene] -N-ethyl-ethaniminium Hydrochloride (Basic Blue No. 7), N- {4-[(4- (dimethylamino) phenyl) 4- (phenylamino) -1-naphthalenyl] methylene} -2,5-cyclohexadien-1-ylidene] -N-methyl-methaniminium hydrochloride (Basic Blue 26), 4-[(4-aminophenyl) (4-imino-2,5-cyclohexadien-1-ylidene) methyl] -2-methyl-aniline- Hydrochloride (Basic Violet 14), N- {3-[(4,5-Dihydro-3-methyl-5-oxo-1-phenyl-1H-pyrazol-4-yl) azo] phenyl} -N, N, N-trimethylammonium hydrochloride (Basic Yellow 57), N- [7-hydroxy-8-[(2-methoxyphenyl) azo] -naphth-2-yl] -N, N, N-trimethylammonium hydrochloride ( Basic Red 76), N- [4-[[4- (dimethylamino) phenyl] [4- (phenylamino) -naphth -1-yl] -methylene] -2,5-cyclohexadien-1-ylidene] -N-methyl-2-methaneiminium hydrochloride (Basic Blue 99), [8-[(4'-amino-2 ' -Nitrophenyl) azo] -7-hydroxy-naphth-2-yl] -trimethylammonium hydrochloride (Basic Brown 16), [8-((4'-amino-3'-nitrophenyl) azo) -7-hydroxy -Naphtho-2-yl] -trimethylammonium hydrochloride (BasicBrown 17), Basic Yellow 87, Basic Red 51 or Basic Orange 31.

More preferred are compounds of formula (1) or (2),
W is at least one of which is optionally substituted with the same or different C ₁ -C ₄ alkyl, imidazolium, pyridinium, benzimidazolium, pyrazolium, and the compound being selected from the benzothiazolium.

のカチオン性の、芳香族の、置換又は非置換の複素環式化合物の基であり、
Z₁、Z₂、Z₃、Z₄、及びZ₅は、互いに独立して、N又は-CH=であり、
R₅、R₆、R₇、R₈、R₉、R₁₀、R₁₁、R₁₂、R₁₃、R₁₄、R₁₅、R₁₆、R₁₇、R₁₈、R₁₉、及びR₂₉は、互いに独立して、水素;ハロゲン;又は飽和若しくは不飽和の、直鎖状若しくは分枝状の、置換若しくは非置換の、又はヘテロ原子が介在若しくは非介在のC₁〜C₁₄アルキル;置換若しくは非置換のフェニル基;カルボン酸基;スルホン酸基;ヒドロキシ;ニトリル;C₁〜C₁₆アルコキシ、(ポリ)-ヒドロキシ-C₂〜C₄-アルコキシ;ハロゲン;スルホニルアミノ;SR₂₀、NHR₂₁;NR₂₂R₂₃₅;OR₂₄;SO₂;COOR₂₅;NR₂₆COR₂₇;又はCONR₂₈であり、並びに
R₂₀、R₂₁、R₂₂、R₂₃、R₂₄、R₂₅、R₂₆、R₂₇、及びR₂₈は、それぞれ互いに独立して、水素;非置換若しくは置換C₁〜C₁₄アルキル、C₂〜C₁₄アルケニル、C₅〜C₁₀アリール、C₅〜C₁₀アリール-(C₁〜C₁₀アルキル)、又は-C₁〜C₁₀アルキル(C₅〜C₁₀アリール)であり、
Anは、アニオンである。 Most preferably,
W is the formula

A cationic, aromatic, substituted or unsubstituted heterocyclic group,
Z ₁ , Z ₂ , Z ₃ , Z ₄ , and Z ₅ are each independently N or —CH═,
R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ , R ₁₉ , and R ₂₉ are independently of one another, hydrogen, halogen, or saturated or unsaturated, linear or branched, substituted or unsubstituted, or C ₁ -C ₁₄ alkyl heteroatoms intervention or non-mediated, substituted or unsubstituted substituted phenyl group; a carboxylic acid group; a sulfonic acid group, hydroxy, nitrile, C ₁ -C ₁₆ alkoxy, (poly) - hydroxy -C ₂ -C ₄ - alkoxy, halogen, sulfonylamino, SR _20, NHR _21; NR ₂₂ R ₂₃₅ ; OR ₂₄ ; SO ₂ ; COOR ₂₅ ; NR ₂₆ COR ₂₇ ; or CONR ₂₈ , and
R ₂₀ , R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ , R ₂₆ , R ₂₇ , and R ₂₈ are each independently of each other hydrogen; unsubstituted or substituted C ₁ -C ₁₄ alkyl, C ₂ a (C ₁ -C ₁₀ alkyl), or -C ₁ -C ₁₀ alkyl (C ₅ -C ₁₀ aryl), - -C ₁₄ alkenyl, C ₅ -C ₁₀ aryl, C ₅ -C ₁₀ aryl
An is an anion.

から選択される化合物である。 Even more preferred is a compound of formula (1) or (2),
A is the base

Is a compound selected from

Most preferred is a compound of formula (1),
A is a group of formula (1a) WN = N-Ar or formula (1b) Ar-N = NW-
p and q and r are 1,
W is a condensed or non-condensed aromatic or non-aromatic heterocyclic ring containing quaternary ammonium, and X ₁ , X ₂ , D, C _sat and C ′ _sat are as in formula (1) It is a defined compound.

Most preferred is a compound of formula (2),
A is a group of the formula (1a) WN = N-Ar- or (1c) Ar-N (R ₄ ) -N = CH-W-
V is-(CH ₂ ) _2-
p is 1,
q is 0,
W is a fused or non-fused aromatic or non-aromatic heterocycle containing quaternary ammonium;
X ₁ , X ₂ , C _sat and C ′ _sat , and R ₄ are compounds defined as in formula (1).

Preferred compounds according to the invention have the formula

[Where
A is a group of the formula (1a) WN = N-Ar- or (1b) Ar-N = NW-
Y ₁ is a biradical selected from phenylene, cyclohexylene, and C ₁ -C ₃ alkylene;
W is a fused or non-fused aromatic or non-aromatic heterocycle containing quaternary ammonium, and
Ar is defined as in equation (1)]
It corresponds to.

Further preferred compounds according to the invention have the formula

[Where
A is a group of the formula (1a) WN = N-Ar- or (1b) Ar-N = NW-
R ₄ is methyl or tert-butyl;
W is a fused or non-fused aromatic or non-aromatic heterocycle containing quaternary ammonium, and
X ₁ and C _sat are defined as in equation (1),
Ar is defined as in equation (1c)]
It corresponds to the compound of

の基である化合物である。 Most preferred are compounds of formula (3) and (4),
A is the formula

It is a compound which is a group.

Aryl or heteroaryl group or an aryl or heteroaryl moiety of groups, may be substituted with at least one substituent mediated by carbon atoms selected from the following: hydroxyl, C ₁ -C ₄ alkoxy, C ₂ -C ₄ (poly) hydroxyalkoxy, acylamino, nitrogen optionally having at least one hydroxyl group, or the same or different two C ₁ -C ₄ amino substituted by alkyl, or two groups that, to which they are attached The possibility of forming an optionally substituted, saturated or unsaturated heterocycle containing 5 to 7 members, such as 5 or 6 members, optionally containing another heteroatom identical or different to nitrogen C ₁ -C _16, such as C ₁ -C ₈ alkyl, optionally substituted with at least one group selected from one; chlorine, fluorine , Or halogen atom such as bromine; hydroxyl; C ₁ -C ₄ alkoxy, C ₂ -C ₄ (poly) hydroxyalkoxy; optionally having at least one group selected from hydroxyl and amino groups, the same or different, One or two C ₁ -C ₄ alkyls, or two optionally substituted C ₁ -C ₃ alkyls, the alkyl group of which is different from or identical to the nitrogen atom to which they are attached, An amino, optionally containing at least one other heteroatom, optionally forming a 5- to 7-membered, optionally substituted saturated or unsaturated heterocycle; the group R is a hydrogen atom and at least one is selected from C ₁ -C ₄ alkyl optionally having hydroxyl group, group R 'is a C ₁ -C ₂ alkyl, acylamino (-NR-COR') groups; the same or different Group R is hydrogen and is selected from C ₁ -C ₄ alkyl optionally having at least one hydroxyl group, a carbamoyl _{((R) 2 N-CO-} ) group; group R is hydrogen and at least one hydroxyl group An alkylsulfonylamino (R′SO ₂ —NR—) group selected from C ₁ -C ₄ alkyl optionally having the group R ′ selected from C ₁ -C ₄ alkyl and phenyl; the same or different groups R is selected from a C ₁ -C ₄ alkyl optionally having a hydrogen atom and at least one hydroxyl group, acidic or chlorinated carboxyl group (such as substituted or unsubstituted with an alkali metal or ammonium) Aminosulfonyl ((R) ₂ N—SO ₂ —) group; nitro group; nitrile (CN) group; trifluoromethyl (CF ₃ ) group. Cyclic or heterocyclic portion of the non-aromatic group may be substituted with at least one substituent mediated by carbon atoms selected from the following groups: hydroxyl, C ₁ -C ₄ alkoxy, C ₂ ~ C ₄ (poly) hydroxyalkoxy, R ′ is selected from C ₁ -C ₄ alkyl optionally having a hydrogen atom and at least one hydroxyl group, and the group R is C ₁ -C ₂ alkyl alkylcarbonylamino ( RCO-NR′-), an amino group optionally substituted with two identical or different C ₁ -C ₄ alkyl groups optionally having at least one hydroxyl group, the alkyl group being a nitrogen atom to which they are attached; Forms an optionally substituted saturated or unsaturated heterocycle containing 5 to 7 members, optionally containing at least one other heteroatom that is different or identical to nitrogen Amino group which may potentially. A hydrocarbon chain is unsaturated when it contains one or more double bonds and / or one or more triple bonds. A heteroaromatic or heteroaryl group is an aromatic group in which at least one of the carbon atoms has been replaced with a heteroatom selected from nitrogen, oxygen, and sulfur.

  Organic dye residues are anthraquinone, acridine, azo, azomethine, hydrazomethine, benzodifuranone, coumarin, diketopyrrolopyrrole, dioxaxin, diphenylmethane, formazan, indigoid, indophenol, naphthalimide, naphthoquinone, nitroaryl, merocyanine, methine, oxazine Perinone, perylene, pyrenequinone, phthalocyanine, phenazine, quinoneimine, quinacridone, quinophthalone, styryl, triphenylmethane, xanthene, thiazine and thioxanthene dyes.

Examples of disulfide dyes of the present invention are described below.

  The dyeing composition useful in the method of the present invention may comprise at least one disulfide dye selected from the dyes of formulas (1) and (2).

  The at least one disulfide dye may be present in the composition in an amount ranging from 0.001 to 50% based on the total weight of the composition. In at least one embodiment, this amount ranges from 0.005 to 20% by weight, such as 0.01 to 5% by weight, relative to the total weight of the composition.

  The dyes of formulas (1) and (2) according to the invention are suitable for dyeing organic materials such as keratin-containing fibers, wool, leather, silk, cellulose or polyamide, cotton or nylon, and preferably human hair. is there. The resulting dyeings are distinguished by their shades of color and their good fastness properties to washing, for example fastness to light, shampoo and friction. The stability of the dyes according to the invention, in particular the storage stability, is excellent.

  The variety of dye shades can be increased by combining with other dyes.

  Therefore, the dyes of the formulas (1) and (2) of the present invention are the same dyes or other types of dyes, in particular direct dyes, oxidation dyes; color former compounds, diazotized compounds or capped diazotized compounds. Combinations of dye precursors; and / or combinations with cationic reactive dyes.

  Direct dyes may be of natural origin or prepared synthetically. Direct dyes are uncharged, cationic or anionic, for example acid dyes.

  The dyes of formulas (1) and (2) may be used in combination with at least one single direct dye different from the dyes of formulas (1) and (2).

  Examples of direct dyes are “Dermatology”, Ch. Culnan, H. Maibach, Verlag Marcel Dekker Inc., New York, Basle, 1986, Vol. 7, Ch. Zviak, “The Science of Hair Care”, 7 "Europaisches Inventar der Kosmetikrohstoffe", published in chapters, 248-250 pages and from the European Commission and available in the form of a disc from the Bundesverband der deutschen Industrie- und Handelsunternehmen fur Arzneimittel, Reformwaren und Korperpflegemittel e. V., Mannheim , 1996.

  In addition, cationic nitroaniline and anthraquinone dyes are useful in combination with dyes of formulas (1) and (2).

  The dyes of formulas (1) and (2) may also be combined with acid dyes, such as those known under the international name (Color Index) or trade names.

  These acid dyes may be used either as a single component or in any combination thereof.

  The dyes of formulas (1) and (2) are also selected from the group of, for example, nitroaniline, nitrophenylenediamine, nitroaminophenol, anthraquinone, indophenol, phenazine, phenothiazine, bispyrazolone, bispyrazole aza derivatives, and methine. Or an uncharged dye.

  Furthermore, the dyes of formulas (1) and (2) may also be used in combination with an oxidative dye system.

  Oxidative dyes that are not dyes but are dye precursors in the initial state are classified into developer and color former compounds according to their chemical properties.

Suitable oxidation dyes are, for example,
DE 19 959 479, in particular, column 2, lines 6 to 3, line 11,
“Dermatology”, Ch. Culnan, H. Maibach, Verlag Marcel Dekker Inc., New York, Basle, 1986, Vol. 7, Ch. Zviak, “The Science of Hair Care”, Chapter 8, pp. 264-267 (oxidation dyes)
It is described in.

  Preferred developer compounds are, for example, primary aromatic amines substituted in the para or ortho position with substituted or unsubstituted hydroxy or amino residues, or diaminopyridine derivatives, heterocyclic hydrazones, 4 -Aminopyrazole derivatives or 2,4,5,6-tetraaminopyrimidine derivatives.

  In addition, a physiologically compatible acid addition salt form of the developer compound such as hydrochloride or sulfate can be used. Developer compounds having an aromatic OH group are also suitable in their salt form with a base, such as alkali metal phenolate.

  Preferred developer compounds are described in DE 19959479, page 2, lines 8-29.

  Preferred color former compounds are disclosed in m-phenylenediamine derivatives, naphthols, resorcin and resorcin derivatives, pyrazolones and m-aminophenol derivatives, and most preferably DE 19959479, page 1, lines 33-3, line 11. The color former compound.

  Furthermore, the autooxidizing compound may be used in combination with a dye of formula (1).

  Auto-oxidizing compounds are aromatic compounds that have more than two substituents in the aromatic ring and have a very low redox potential and are therefore oxidized when exposed to air. The dyeings obtained with these compounds are very stable and resistant to hair washing.

  Autooxidizing compounds are, for example, benzene, indole or indole, in particular 5,6-dihydroxyindole or 5,6-dihydroxyindole.

  The dyes of formula (1) are also henna red, henna neutral, henna black, camomile blossom, sandalwood, black tea, Natural such as Rhamnus frangula bark, sage, campeche wood, madder root, catechu, sedre, and alkanet root May be used in combination with a dye present in

  Furthermore, the dyes of formula (1) and (2) may also be used in combination with capped diazotized compounds.

  Suitable diazotized compounds are for example the compounds of the formulas (1) to (4) in WO 2004/019897 (bridging gages 1 and 2) and the corresponding one disclosed on page 3 of the reference Water-soluble coupling components (I) to (IV).

More preferred dyes or dye combinations useful for the combination with the dye of formula (1) according to the invention are:
(DC-01): WO95 / 01772, a mixture of at least two cationic dyes, in particular page 2, line 7 to page 4, line 1, preferably page 4, line 35 to page 8, line 21 The formulation is described on page 11, last section to page 28, line 19.

(DC-02): US 6,843,256, cationic dyes, especially compounds of formulas (1), (2), (3), and (4) (column 1, line 27 to column 3, line 20) And preferably the compounds prepared in Examples 1 to 4 (column 10, line 42 to column 13, line 37, the formulation is column 13, line 38 to column 15, 8 It is disclosed on the line.

(DC-03): EP 970 685, direct dyes, especially on page 2, lines 44-9, line 56, preferably on page 9, lines 58-48, line 12, keratin-containing fibers Methods for dyeing are described in particular on page 50, lines 15 to 43, and formulations are described on page 50, lines 46 to 51, line 40.

(DC-04): DE-A-19 713 698, direct dyes, especially on page 2, lines 61 to 3, line 43, formulation on pages 5, lines 26 to 60 ,Have been described.

(DC-05): US 6,368,360, direct dyes (column 4, lines 1 to 6, line 31) and oxidizing agents (column 6, lines 37 to 39) are disclosed, Formulations are disclosed in column 7, line 47 to column 9, line 4.

(DC-06): EP 1 166 752, cationic dyes (page 3, lines 22-4, line 15) and anionic UV absorbers (page 4, lines 27-30) are disclosed The formulation is disclosed on page 7, line 50 to page 9, line 56.

(DC-07): EP 998,908, an oxidative staining (page 2, lines 48 to 4, line 1) comprising a cationic direct dye and pyrazolo- [1,5-a] -pyrimidine is disclosed, Dyeing formulations are disclosed on page 47, line 25 to page 50, line 29.

(DC-08): FR-2788432, combination with cationic dye Arianor, especially on page 53, line 1 to page 63, line 23, more particularly on pages 51 to 52, most particularly Basic Brown 17, Basic Brown 16, Basic Red 76 and Basic Red 118, and / or at least one basic yellow 57, and / or at least one basic blue 99; or a combination of arianor and / or oxidative dye, especially page 2, line 16 From page 3 to page 16, line 16 the staining formulation is disclosed on page 53, line 1 to page 63, line 23.

(DC-09): DE-A-19 713 698, combinations of direct dyes with oxidants, oxidative dyes, and permanent wave fixers containing direct dyes, especially on page 4, lines 65-5, 59 It is disclosed on the line.

(DC-10): EP 850 638, developer compound and oxidizing agent, especially on page 2, line 27 to page 7, line 46, preferably page 7, line 20 to page 9, line 26 The dyeing composition is 2 pages, 3rd to 12th lines, and 30th to 14th pages, and 28th page, 35th to 30th pages, 20th line, preferably 30th page, 25th to 32th lines. Disclosed on page 30, line 30.

(DC-11): US 6,190,421, instant formulation of composition (A), organic powder excipient and / or inorganic containing one or more oxidative dye precursors and optionally one or more color formers Instant formulation of composition (B) in powder form, containing one or more direct dyes, optionally dispersed in a powdered excipient (column 5, lines 40-7, column 14, Line), as well as a composition (C) containing one or more oxidizing agents, and the formulation is disclosed in column 8, lines 60-9, line 56.

(DC-12): US 6,228,129, at least one oxidizing base, at least one cationic direct dye, and at least one enzyme of the two-electron oxidoreductase type, at least one for said enzyme The ready-to-use composition comprising, in the presence of a donor, in particular, column 8, lines 17 to 13, line 65, dyeing composition, column 2, lines 16 to 25 In the column, line 55, the multi-compartment staining device is described in column 26, lines 13-24.

(DC-13): WO99 / 20235, composition of at least one cationic dye and at least one nitrated benzene dye having a cationic direct dye and a nitrobenzene direct dye, page 2, lines 1-7 , Lines 9 and 39, lines 1 to 40, line 11, preferably page 8, lines 12 to 25, line 6, page 26, lines 7 to 30, page 15; 1st page, 25th line to 8th page, 5th line, 30th page, 17th line to 34th page, 25th line, 8th page, 12th line to 25th page, 6th line, 35th page, 21st line to 27th Lines, especially page 36, lines 1 to 37.

(DC-14): WO99 / 20234, compositions comprising at least one direct cationic dye and at least one autooxidizing dye, in particular benzene, indole, and indole derivatives, are described, preferably the direct dye is Page 2, lines 19-26, line 4, auto-oxidizing dyes are disclosed in particular on page 26, lines 10, page 28, line 15, dyeing formulations, in particular 34 Page, 5th line to 35th page, 18th line.

(DC-15): EP 850 636, an oxidation dyeing composition comprising at least one direct dye and at least one meta-aminophenol derivative and at least one developer compound and an oxidizing agent as a color former component In particular, on page 5, line 41 to page 7, line 52, the dyeing composition is disclosed on page 19, line 50 to page 22, line 12.

(DC-16): EP-A-850 637, at least one oxide base selected from para-phenylenediamine and bis (phenyl) alkylenediamine, and acid addition salts thereof, meta-diphenol and its acid An oxidation dyeing composition comprising at least one color former selected from addition salts, at least one cationic direct dye, and at least one oxidizing agent, in particular, page 6, lines 50 to 8, On line 44, the staining formulation is disclosed on page 21, lines 30-22, line 57.

(DC-17): WO99 / 48856, an oxidative dyeing composition comprising a cationic color former, especially page 9, lines 16 to 13, lines 8 and 11, lines 20 to 12, page 13 On line, the staining formulation is disclosed on page 36, lines 7-39, line 24.

(DC-18): DE 197 172 24, unsaturated aldehydes and color former compounds and primary and secondary amino group compounds, nitrogen-containing heterocyclic compounds, amino acids, oligopeptides, aromatic hydroxy compounds, and / or at least one of Staining agents containing CH-active compounds are disclosed on page 3, lines 42-5, line 25 and staining formulations are disclosed on page 8, lines 25-9, line 61.

  In the dye combinations disclosed in the above references (DC-01 to DC-18), the dye of formula (1) according to the invention may be added to the dye combination or dyeing formulation, or It may be replaced by at least one dye of formula (1).

  The dyeing composition may further comprise at least one oxidized base and / or at least one color former conventionally used for dyeing dyed keratin fibers.

  Oxidized bases can include paraphenylenediamine, bisphenylalkylenediamine, para-aminophenol, bis-para-aminophenol, ortho-aminophenol, heterocyclic bases, and addition salts thereof.

  Examples of color formers include meta-phenylenediamine, meta-aminophenol, meta-diphenol, naphthalene color former, heterocyclic color former, and addition salts thereof.

  Each of the color formers is generally present in an amount ranging from 0.001 to 10% by weight relative to the total weight of the dyeing composition, such as 0.005 to 6%.

  The oxidized base present in the dyeing composition is generally present in an amount ranging from 0.001 to 10% by weight relative to the total weight of the dyeing composition, such as 0.005 to 6% by weight.

  In general, oxidation base and color former addition salts that can be used in the present invention include hydrochloride, hydrobromide, sulfate, citrate, succinate, tartrate, lactate, tosylate, benzenesulfonate, For example, selected from addition salts with acids such as phosphates and acetates, and addition salts with bases such as sodium hydroxide or potassium hydroxide, aqueous ammonia, amines or alkali metal hydroxides such as alkanolamines Is done.

  Suitable media for dyeing are also cosmetic media, also called dye carriers, which generally comprise water or a mixture of water and at least one organic solvent.

As organic solvents, such as lower C ₁ -C ₄ alkanols such as ethanol and isopropanol; 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether, and polyols and polyol ethers such as monomethyl ether, and benzyl alcohol Or aromatic alcohols such as phenoxyethanol, and mixtures thereof.

  The solvent, if present, may be present in an amount in the range of 1-40% by weight relative to the total weight of the dyeing composition, such as 5-30% by weight.

  The staining composition can also be an anionic, cationic, nonionic, amphoteric or zwitterionic surfactant or mixture thereof, anionic, cationic, nonionic, amphoteric. Or inorganic or organic thickeners such as zwitterionic polymers and mixtures thereof, anionic, cationic, nonionic and amphoteric associative polymer thickeners, antioxidants, penetrants, Hair, such as sequestering agents, fragrances, buffers, dispersants, modifiers such as modified or non-modified volatile or non-volatile silicones, film formers, ceramides, preservatives, and opacifiers May contain at least one adjuvant conventionally used in compositions for dyeing.

  The above adjuvants are generally present for each in an amount ranging from 0.01 to 20% by weight relative to the total weight of the composition.

  The composition may also comprise at least one other additional disulfide compound that is different from the compound corresponding to formula (1) or (2).

As a guide, the disulfide is optionally substituted with a heteroatom and at least one saturated or unsaturated, linear or branched, optionally intervening with neutralized or non-neutralized carboxyl groups. C ₅ -C ₃ may be selected from compounds containing at least one fatty chain such as a hydrocarbon chain.

Examples of this class of compounds include dimers of thioglycolic acid and CH _3- (CH ₂ ) ₁₇ -SS- (CH ₂ ) ₁₇ -CH ₃ or CH _3- (CH ₂ ) -SS- (CH ₂ ) Mention may be made of its derivatives of the _{1O 2} —CH ₃ type.

  At least one additional disulfide compound, if present, is present in an amount ranging from 0.001 to 10% by weight relative to the weight of the composition.

  Of course, those skilled in the art will recognize this or these such that the advantageous properties inherently associated with the dyeing composition according to the invention are not impaired or substantially impaired by the anticipated adduct (s). Any additional compounds of will be carefully selected.

  The pH of the staining composition may be in the range of 3-14, such as 5-11. The pH may be adjusted to the desired value by acidifying or alkalizing agents commonly used to dye keratin fibers, or alternatively, using conventional buffer systems. Examples of the acidifying agent include carboxylic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, acetic acid, tartaric acid, citric acid, and lactic acid, and inorganic or organic acids such as sulfonic acid.

Among the alkalizing agents, ammonia water, alkali metal carbonates, alkanolamines such as mono-, di-, and triethanolamine and their derivatives, sodium or potassium hydroxide, and the following formula

[Where
R is a propylene residue, which may be substituted with OH or C ₁ -C ₄ alkyl,
R ₃ , R ₄ , R ₅ , and R ₆ , independently or independently of one another, are hydrogen, C ₁ -C ₄ alkyl, or hydroxy- (C ₁ -C ₄ ) alkyl]
As an example,

  The dyeing composition may be provided in various forms, such as liquid form, cream form, gel form, or any other suitable form for dyeing keratin fibers such as hair.

  According to one embodiment, the method of the present invention includes pretreatment with a reducing agent capable of reducing disulfide bonds.

  The reducing agent is for example selected from thiols such as thioglycolic acid, cysteine, homocysteine, thiolactic acid, salts of these thiols, phosphines, bisulfites and sulfites.

  This reducing agent also includes, for example, borohydrides and their derivatives such as borohydrides, cyanoborohydrides, triacetoxyborohydrides, and trimethoxyborohydride salts: sodium, lithium, potassium, calcium, and quaternary ammonium (tetramethylammonium, Tetraethylammonium, tetra-n-butylammonium, benzyltriethylammonium) salt; may be selected from catecholborane.

  This pretreatment may be for a short time, 0.1 seconds to 30 minutes, for example 0.1 seconds to 5 minutes, depending on the reducing agents listed above.

  Application of the dyeing composition is generally carried out at room temperature. However, the application may be carried out at a temperature in the range of 20-100 ° C.

  According to one embodiment, the reducing agent is added to the dyeing composition at the time of use.

  According to another embodiment, the application of the staining composition may be followed by a short reduction step of 0.1 seconds to 30 minutes, such as 0.1 seconds to 5 minutes, with a thiol or borohydride type reducing agent as described above.

  According to another embodiment, the staining composition may comprise at least one oxidizing agent, so that the composition is said to be “ready for use”.

  In at least one embodiment, the composition is obtained by mixing the composition according to the present disclosure with an oxidizing composition before being applied to the keratin material to be treated.

  The oxidizing agent may be any oxidizing agent conventionally used in the art. Thus, the oxidizing agent is selected from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborate and persulphate, and enzymes, in which the peroxidase, Mention may be made of oxidoreductases containing two electrons such as uricase and oxygenated enzymes containing four electrons such as laccase. In at least one embodiment, the oxidant is hydrogen peroxide.

  The amount of oxidant in the composition ranges from 1 to 40% by weight relative to the weight of the ready-to-use composition, such as 1 to 20% by weight relative to the weight of the ready-to-use composition.

  In general, the oxidizing composition used is an aqueous composition and may be in the form of a solution or also an emulsion.

  Usually, the dyeing composition which does not contain an oxidizing agent is mixed in an equivalent weight of 0.5 to 10% by weight of the oxidizing composition.

  It should be pointed out that the pH of the ready-to-use composition is 4-12, for example 7-11.5.

  Application of the dyeing composition may be followed by an oxidizing post-treatment, or an adjusting post-treatment optionally combined with an oxidizing post-treatment.

  Also disclosed herein is a multi-compartment device or dyeing “kit”, in which the first compartment contains at least one disulfide dye of formula (1) or (2). The second compartment contains a reducing agent capable of reducing the disulfide bonds of the dye.

  One of these compartments may additionally contain at least one other dye selected from direct dyes and oxidation dyes, provided that the disulfide dyes useful herein and the at least one dye are Other dyes of the species are not in the same compartment of the kit.

  The invention also relates to a multi-compartment device, wherein the first compartment comprises a dyeing composition comprising at least one disulfide dye of formula (1) or (2), and the second compartment comprises a dye A reducing agent capable of reducing disulfide bonds is included, and the third compartment contains an oxidizing agent.

  Each of the aforementioned devices may comprise means capable of delivering the desired mixture to the hair, for example the device described in FR 2586913.

  The following examples serve to illustrate the method of staining without limiting the method. Unless otherwise specified, parts and percentages relate to weight. The amount of dye defined is related to the material to be colored.

  T, s, d, q, and J define NMR spectral values, t is a triplet, s is a singlet, d is a doublet, q is a quadruple, J Is the coupling constant.

A. Preparation Examples Example A1:

  An orange suspension of 1.1 g Z-9448 (MW: 342.38) and 11.4 g 1,4-diaminocyclohexane in 40 ml 2-propanol is stirred for 5 hours at 60 ° C. After cooling at room temperature, the dark red solution is diluted with 100 ml of 2-propanol and filtered. The isopropanol solution is precipitated with 600 ml of t-butyl methyl ether, washed with TBME and dried at 50 ° C. to give 5.23 g of compound 1.

LC-MS: m / z = 501; λ _max = 514nm

  To a suspension of 0.5 g lipoic acid (206.33) in 4 ml dichloromethane is added 0.34 g thionyl chloride (MW: 118.97). The reaction mixture becomes soluble. After stirring for 1 hour at room temperature, the yellow solution is added at 40 ° C. to a solution of 0.84 g of compound 1 (MW: 348.88) and 0.72 g of triethylamine (MW: 101.19) in 30 ml of dimethylacetamide. After stirring for 2 hours at 40 ° C., the reaction mixture is cooled to room temperature and precipitated into 150 ml of ethyl acetate. The dark red powder is dried at 50 ° C. Product 2 is purified by column chromatography.

Example A2:

  178822-03-2 (Compound 3) is prepared as described in EP 1219683.

  To a suspension of 0.32 g of lipoic acid (206.33) in 4 ml of dichloromethane is added 0.24 g of thionyl chloride (MW: 118.97). The reaction mixture becomes soluble. After stirring for 1 hour at room temperature, the yellow solution is added at 40 ° C. to a solution of 0.31 g of compound 3 (MW: 307.38) in 20 ml of dimethylacetamide. After stirring for 2 hours at 40 ° C., the reaction mixture is cooled to room temperature and precipitated into 150 ml of ethyl acetate. The dark powder is dried at 50 ° C. The product is purified by column chromatography to give 280 mg of dark, sticky product.

LC-MS: m / z = 495; λ _max = 526nm
Example A3:

  Lipoic acid (MW206.33) 2.063 g is solubilized in 10 ml DCM and cooled in an ice and acetone bath. 1.13 g of thionyl chloride (MW118.97) is added dropwise at −8 ° C. for 30 minutes. The reaction mixture is stirred for 1 hour at room temperature.

  In a second flask, 1.64 g of compound 7 (MW327.26) is solubilized in 25 ml of DMI and 4.048 g of triethylamine (MW101.19) is added. The lipoic acid chloride solution above is added for 10 minutes and the reaction mixture is stirred at room temperature for 90 minutes. The reaction mixture is precipitated with 200 ml of acetone and filtered. The filtrate was taken up in 2 ml of DMI, dried over sodium sulfate and recrystallized in 100 ml of acetone, yielding 1.96 g of product 8.

LC-MS: m / z = 445; λ _max = 422nm
Example A4

  Under a nitrogen atmosphere, 1.54 g of thionyl chloride (MW: 118.97) is added to a suspension of 2.06 g of lipoic acid (206.33) in 20 ml of dichloromethane. The reaction mixture becomes soluble. After stirring for 1 hour at room temperature, the yellow solution is added to a solution of 1.65 g N, N diethyl-benzene-1,3 diamine (CAS: 26513-20-2) (MW164.25) in 10 ml THF. The reaction mixture is cooled to 10 ° C. and 3.3 g of triethylamine is added dropwise within 15 minutes. The reaction mixture is then warmed to room temperature, diluted with 50 ml of dichloromethane and extracted with 50 ml of 5% aqueous HCl. The organic phase is dried over sodium sulfate and evaporated to dryness to give 2.9 g of the expected compound 9.

  1.4 g 4-amino-1,2-dimethyl-quinolinium (MW284.43) is solubilized in 15 ml formic acid and 20 ml acetic acid. 1.4 g of nitric sulphuric acid 40% (MW127.1) is added dropwise at 0-5 ° C. within 5 minutes. After 2 hours of diazotization at 0 ° C., the reaction mixture is dark yellow. This solution is slowly added at 0 ° C. to a solution of 1.76 g of compound 9 in 30 ml of NMP and allowed to stir at this temperature for 2 hours. Next, 15 ml of sodium hydroxide 4N is added and left overnight. The dark blue suspension is filtered and washed with water / methanol (1/1).

  The mixture is purified by filtration on silica gel (eluent THF / methanol, 1/5). 100 mg of dark, sticky product 10 is obtained.

LC-MS: m / z = 536; λ _max = 596nm
B. Application ExamplesIn the following application examples, compositions within the following definitions are used:
Solution 1 (Permanent lotion, pH 8.2)
Water, ammonium thioglycolate, ammonium bicarbonate, ethoxydiglycol, hexylene glycol, thioglycolic acid; thiolactic acid, PEG-60 hydrogenated castor oil, glycine, etidronic acid, isocetes-20, polysilicone-9, styrene / PVP copolymer, Trideceth-12, Amodimethicone, Cetrimonium chloride, Ammonium hydroxide, Polyquaternium-6, Isopropyl alcohol, Modified alcohol, Simethicone, Fragrance
Solution 2 (permanent fixing solution, pH 3.9)
Based on:
Water, hydrogen peroxide, propylene glycol, lauryldimonium hydroxypropyl hydrolyzed wheat protein, PEG-5 cocamide, sodium cocoamphoacetate, polyquaternium-35, cocobetaine, acetaminophen, phosphoric acid, sodium chloride, flavor
Example B1
0.2% (abs.) Of dye A1 is dissolved in a 5% solution of a nonionic surfactant (Plantacare 200UP, Henkel) adjusted to pH 9.5 with citric acid and monoethanolamine.

  This red dyeing solution is applied to dry hair (two blondes, two damaged and two 90% gray hair strands) and left at room temperature for 20 minutes. The strand is then rinsed with tap water and dried for 12 hours.

Example B2
Apply Solution 1 (Permanent Lotion) to shampooed hair (two blondes, two damaged and two 90% gray hair strands) and let stand for 10 minutes. The strands are then rinsed with tap water and the towel-dried strands are treated with the 0.2% by weight colored material solution of Example B1, allowed to stand for 20 minutes, and then rinsed. Next, the towel-dried strand is treated with Solution 2 (permanent fixation) and allowed to stand for 10 minutes. The strand is then rinsed with tap water and dried at room temperature for 12 hours.

Example B3
0.1% (abs.) Of dye A2 is dissolved in a 5% solution of a nonionic surfactant (Plantacare 200UP, Henkel) adjusted to pH 9.5 with citric acid and monoethanolamine.

  This red dyeing solution is applied to dry hair (two blondes, two middle blondes, two damaged and two 90% gray hair strands) and left at room temperature for 20 minutes. The strand is then rinsed with tap water and dried for 12 hours.

Example B4
Solution 1 (permanent lotion) is applied to shampooed hair (two blondes, two middle blondes, two damaged and two 90% gray hair strands) and allowed to stand for 10 minutes. The strands are then rinsed with tap water and the towel-dried strands are treated with the 0.2% by weight colored material solution of Example B1, allowed to stand for 20 minutes, and then rinsed. Next, the towel-dried strand is treated with Solution 2 (permanent fixation) and allowed to stand for 10 minutes. The strand is then rinsed with tap water and dried at room temperature for 12 hours.

Example B5
50 parts of chemically bleached beech sulfite was added to 50 parts of bleached RKN15 in water (pH 6, water hardness 10 ° German hardness, temperature 20 ° and liquid ratio 40: 1). Mixing with beating degree 22DEG SR) and 2 parts of the dye from Example A1. After stirring for 15 minutes, the paper sheet is made with a Frank-sheet-former.

  The paper was dyed in a very strong red shade. The effluent is completely colorless. Almost 100 percent exhaustion is obtained. The fastness properties against light and wet processing are very good.

Example B6
A paper web made of bleached beech sulphite pulp (22DEG SR) is produced on a laboratory paper machine operating continuously. The aqueous dye solution from Example A2 is continuously weighed into the low density pulp 10 seconds upstream of the head box with vigorous stirring (0.5 percent dyeing, liquid ratio 400: 1, water hardness is (German hardness 10 °, pH 6, temperature 20 °).

  A medium intensity deep reddish purple coloration is formed on the web. The effluent is completely colorless.

Example B7
10 parts of cotton fabric (decolorized and mercerized cotton) are dyed with a laboratory beam dyeing machine in 200 parts of liquid containing 0.05 part of the dye according to Example A1 (water hardness is 10 in German hardness). °, pH 4, the dye liquor circulates 3 times per minute). The temperature is raised from 20 degrees to 100 degrees during 60 minutes and then held constant for 15 minutes.

  The dyeing solution is completely exhausted. A deep red coloration is formed on the cotton fabric that is distinguished by good fastness to light and very good fastness to wet processing.

  Dye a woven fabric made of recycled (viscose) using the same procedure The dye of Example A1 gives a deep red dyeing which again has good fastness to light and very good fastness to wet processing.

Example B8 of wood colorant containing pure solvent:
3.0 parts by weight of dye A1
40.0 parts by weight of ethyl alcohol,
40.0 parts by weight of 1 methoxy-2-propanol and
17.0 parts by weight of isopropanol.

Example B9 of an aqueous wood colorant:
3.0 parts by weight of dye A1 is dissolved in 100.0 ml of water containing 0.05 weight percent Invadin LU (wetting agent).

[式中、
Aは、カチオン染料の残基から選択され、
X ₁ 及びX ₂ は、-N(R ₁ )-、N ⁺ (R ₁ )(R ₂ )-、-O-、-S-、-CO-、-SO ₂ -から選択される少なくとも一つの二価の基が場合によって介在する、及び/又は少なくとも一つの同一の若しくは異なるヘテロ原子を場合によって含む、場合によって置換された、飽和若しくは不飽和の、縮合若しくは非縮合の、芳香族若しくは非芳香族(複素)環式基が場合によって介在する、飽和又は不飽和のC ₁ 〜C ₃₀ 炭化水素鎖から、互いに独立して選択され、
Vは、ヒドロキシによって場合によって置換されたC ₁ 〜C ₃ アルキレンであり、
Dは、-N(CO)-R ₃ から選択される基であり、
C _sat 及びC' _sat は、互いに独立して、場合によって置換された、場合によって環式、直鎖状、又は分枝状のC ₁ 〜C ₁₈ アルキレン鎖であり、
R ₁ 及びR ₂ は、水素、C ₁ 〜C ₄ アルキル、ヒドロキシアルキル、又はアミノアルキルから、互いに独立して選択され、
R ₃ は、C ₁ 〜C ₄ アルキルであり、
p、q、及びrは、互いに独立して、0又は1である]
の化合物。
（２）Aが、式(1a)W-N=N-Ar-、(1b)Ar-N=N-W-、及び(1c)Ar-N(R ₄ )-N=CH-W-
[式中、
Wが、第四級アンモニウムを含む、縮合又は非縮合の芳香族又は非芳香族の複素環であり、
Arが、少なくとも一つのハロゲン原子、少なくとも一つのアルキル基、少なくとも一つのヒドロキシル基、少なくとも一つのアルコキシ基、少なくとも一つのヒドロキシアルキル基、又は少なくとも一つのアミノ基若しくは(ジ)アルキルアミノ基で場合によって置換されている、C ₅ 又はC ₆ アリール基及びナフチル型の芳香族の二環から選択され、
R ₄ が、水素又はC ₁ 〜C ₄ アルキルである]
の基である、(1)に記載の化合物。
（３）Wが、少なくとも一つの同一の又は異なるC ₁ 〜C ₄ アルキルで場合によって置換されている、イミダゾリウム、ピリジニウム、ベンズイミダゾリウム、ピラゾリウム、チアゾリウム、及びベンゾチアゾリウムから選択される、(2)に記載の化合物。
（４）Wが、式

[Z ₁ 、Z ₂ 、Z ₃ 、Z ₄ 、及びZ ₅ は、互いに独立して、N又は-CH=であり、
R ₅ 、R ₆ 、R ₇ 、R ₈ 、R ₉ 、R ₁₀ 、R ₁₁ 、R ₁₂ 、R ₁₃ 、R ₁₄ 、R ₁₅ 、R ₁₆ 、R ₁₇ 、R ₁₈ 、R ₁₉ 、及びR ₂₉ は、互いに独立して、水素;ハロゲン;又は飽和若しくは不飽和の、直鎖状若しくは分枝状の、置換若しくは非置換の、又はヘテロ原子が介在若しくは非介在のC ₁ 〜C ₁₄ アルキル;置換若しくは非置換のフェニル基;カルボン酸基;スルホン酸基;ヒドロキシ;ニトリル;C ₁ 〜C ₁₆ アルコキシ、(ポリ)-ヒドロキシ-C ₂ 〜C ₄ -アルコキシ;ハロゲン;スルホニルアミノ;SR ₂₀ 、NHR ₂₁ ;NR ₂₂ R ₂₃ ;OR ₂₄ ;SO ₂ ;COOR ₂₅ ;NR ₂₆ COR ₂₇ ;又はCONR ₂₈ であり、
R ₂₀ 、R ₂₁ 、R ₂₂ 、R ₂₃ 、R ₂₄ 、R ₂₅ 、R ₂₆ 、R ₂₇ 、及びR ₂₈ は、それぞれ互いに独立して、水素、非置換若しくは置換C ₁ 〜C ₁₄ アルキル、C ₂ 〜C ₁₄ アルケニル、C ₅ 〜C ₁₀ アリール、C ₅ 〜C ₁₀ アリール-(C ₁ 〜C ₁₀ アルキル)、又は-C ₁ 〜C ₁₀ アルキル(C ₅ 〜C ₁₀ アリール)であり、
Anがアニオンである]
のカチオン性の、芳香族の、置換又は非置換の複素環式化合物の基である、(1)〜(3)のいずれかに記載の化合物。
（５）Aが、基

から選択される、(1)〜(4)のいずれかに記載の化合物。
（６）式(1)において、
Aが、式(1a)W-N=N-Ar-又は(1c)Ar-N(R ₄ )-N=CH-W-の基であり、
Vが、-(CH ₂ ) ₂ -であり、
pが、1であり、
qが、0であり、
Wが、第四級アンモニウムを含む、縮合又は非縮合の、芳香族又は非芳香族の複素環であり、
X ₁ 、X ₂ 、C _sat 、C' _sat 、及びR ₄ が、(1)の通り定義される、(1)〜(5)のいずれかに記載の化合物。
（７）式(2)において、
Aが、式(1a)W-N=N-Ar-又は(1c)Ar-N(R ₄ )-N=CH-W-の基であり、
Vが、-(CH ₂ ) ₂ -であり、
pが、1であり、
qが、0であり、
X ₁ 、X ₂ 、C _sat 、C' _sat 、及びR ₄ が、(1)の通り定義され、
Wが、(2)の通り定義される、(1)〜(5)のいずれかに記載の化合物。
（８）式

[式中、
Aは、式(1a)W-N=N-Ar-又は(1b)Ar-N=N-W-の基であり、
Y ₁ は、フェニレン、シクロヘキシレン、及びC ₁ 〜C ₃ アルキレンから選択される二価の基であり、
Wは、第四級アンモニウムを含む、縮合又は非縮合の、芳香族又は非芳香族の複素環であり、
Arは、(2)の通り定義される]
の化合物に相当する、(1)〜(4)のいずれかに記載の化合物。
（９）式

[式中、
Aは、式(1a)W-N=N-Ar-又は(1b)Ar-N=N-W-の基であり、
R ₄ は、メチル又はtert-ブチルであり、
Wは、第四級アンモニウムを含む、縮合又は非縮合の、芳香族又は非芳香族の複素環であり、
X ₁ 、C _sat は、(1)の通り定義され、
W及びArは、(2)の通り定義される]
の化合物に相当する、(1)〜(5)のいずれかに記載の化合物。
（１０）Aが、式

の基である、(8)又は(9)に記載の化合物。
（１１）ヒトケラチン繊維を染色する方法であって、(1)に記載の式(1)又は(2)の染料から選択される少なくとも1種のジスルフィド染料を適切な化粧媒体中に含む染色組成物を、前記繊維に施用するステップを含む、方法。
（１２）染色組成物が、少なくとも1種の還元剤をさらに含む、(11)に記載の方法。
（１３）染色組成物を施用する前に、少なくとも1種の還元剤でケラチン繊維を前処理するステップを含む、(11)又は(12)に記載の方法。
（１４）染色組成物を施用した後に、少なくとも1種の還元剤でケラチン繊維を処理する(後処理)ステップを含む、(11)から(13)のいずれかに記載の方法。
（１５）少なくとも1種の還元剤が、チオール、ホスフィン、重亜硫酸塩、及び亜硫酸塩から選択される、(14)に記載の方法。
（１６）少なくとも1種の還元剤が、チオグリコール酸、システイン、ホモシステイン、チオ乳酸、及びこれらのチオールの塩から選択される、(15)に記載の方法。
（１７）少なくとも1種の還元剤が、チオール、ホスフィン、重亜硫酸塩、及び亜硫酸塩から選択される、(16)に記載の方法。
（１８）少なくとも1種の還元剤が、チオグリコール酸、システイン、ホモシステイン、チオ乳酸、及びこれらのチオールの塩から選択される、(17)に記載の方法。
（１９）染色組成物が、少なくとも1種の酸化剤をさらに含む、(11)から(18)のいずれかに記載の方法。
（２０）少なくとも1種の酸化剤でケラチン繊維を後処理するステップを含む、(11)から(19)のいずれかに記載の方法。
（２１）少なくとも1種の調整剤でケラチン繊維を後処理するステップ、及び場合によってまた、少なくとも1種の酸化剤でケラチン繊維を後処理するステップを含む、(11)から(20)のいずれかに記載の方法。
（２２）酸化剤が、過酸化水素、過酸化尿素、アルカリ金属臭素酸塩、過酸基塩、及び酵素から選択される、(21)に記載の方法。
（２３）式(1)又は(2)の少なくとも1種のジスルフィド染料が、組成物の総重量に対して0.001〜50重量%の範囲の量で染色組成物中に存在する、(11)から(22)のいずれかに記載の方法。
（２４）式(1)及び(2)の染料から選択される少なくとも1種のジスルフィド染料を、適切な化粧媒体中に含む染色組成物。
The wood colorant obtained according to Examples B8 and B9 above is applied 10 times to a 5.5 cm piece of ash wood with a brush. Air-dry the colored pieces of wood for 12 hours.
The following is one of the embodiments of the present invention.
(1) Formula
(1) A- (X ₁ ) _p- (C _sat ) _r -SS- (C _sat ) _q- (X ₂ ) _p -D
Or expression

[Where
A is selected from the residues of cationic dyes;
X ₁ and X ₂ are at least one selected from -N (R ₁ )-, N ⁺ (R ₁ ) (R ₂ )-, -O- , -S-, -CO-, -SO _2- . An optionally substituted, saturated or unsaturated, fused or non-fused, aromatic or non-aromatic, optionally intervened by a divalent group and / or optionally containing at least one identical or different heteroatom family (heterocyclic) ring group is interposed optionally from C ₁ -C ₃₀ hydrocarbon chain, saturated or unsaturated, selected independently of one another,
V is C ₁ -C ₃ alkylene optionally substituted by hydroxy,
D is a group selected from -N (CO) -R ₃ ;
C _sat and C ′ _sat are, independently of one another, optionally substituted, optionally cyclic, linear or branched C ₁ -C ₁₈ alkylene chains;
R ₁ and R ₂ are independently selected from hydrogen, C ₁ -C ₄ alkyl, hydroxyalkyl, or aminoalkyl;
R ₃ is C ₁ -C ₄ alkyl;
p, q, and r are each independently 0 or 1]
Compound.
(2) A is represented by the formula (1a) WN = N-Ar-, (1b) Ar-N = NW-, and (1c) Ar-N (R ₄ ) -N = CH-W-
[Where
W is a fused or non-fused aromatic or non-aromatic heterocycle containing quaternary ammonium;
Optionally Ar is at least one halogen atom, at least one alkyl group, at least one hydroxyl group, at least one alkoxy group, at least one hydroxyalkyl group, or at least one amino group or (di) alkylamino group; Selected from substituted C ₅ or C ₆ aryl groups and naphthyl-type aromatic bicycles;
R ₄ is hydrogen or C ₁ -C ₄ alkyl]
The compound according to (1), which is a group of
(3) W is is optionally substituted with at least one identical or different C ₁ -C ₄ alkyl, imidazolium, pyridinium, benzimidazolium, pyrazolium, chosen thiazolium, and benzothiazolium, The compound according to (2).
(4) W is the formula

[Z ₁ , Z ₂ , Z ₃ , Z ₄ , and Z ₅ are each independently N or —CH═,
R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ , R ₁₉ , and R ₂₉ are independently of one another, hydrogen, halogen, or saturated or unsaturated, linear or branched, substituted or unsubstituted, or C ₁ -C ₁₄ alkyl heteroatoms intervention or non-mediated, substituted or unsubstituted substituted phenyl group; a carboxylic acid group; a sulfonic acid group, hydroxy, nitrile, C ₁ -C ₁₆ alkoxy, (poly) - hydroxy -C ₂ -C ₄ - alkoxy, halogen, sulfonylamino, SR _20, NHR _21; NR ₂₂ R ₂₃ ; OR ₂₄ ; SO ₂ ; COOR ₂₅ ; NR ₂₆ COR ₂₇ ; or CONR ₂₈ ,
R ₂₀ , R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ , R ₂₆ , R ₂₇ , and R ₂₈ are each independently of each other hydrogen, unsubstituted or substituted C ₁ -C ₁₄ alkyl, C ₂ a (C ₁ -C ₁₀ alkyl), or -C ₁ -C ₁₀ alkyl (C ₅ -C ₁₀ aryl), - -C ₁₄ alkenyl, C ₅ -C ₁₀ aryl, C ₅ -C ₁₀ aryl
An is an anion]
The compound according to any one of (1) to (3), which is a group of a cationic, aromatic, substituted or unsubstituted heterocyclic compound.
(5) A is the group

The compound according to any one of (1) to (4), which is selected from:
(6) In equation (1),
A is a group of the formula (1a) WN = N-Ar- or (1c) Ar-N (R ₄ ) -N = CH-W-
V is, - (CH _{2) 2} - and is,
p is 1,
q is 0,
W is a fused or non-fused aromatic or non-aromatic heterocycle containing quaternary ammonium;
The compound according to any one of (1) to (5), wherein X ₁ , X ₂ , C _sat , C ′ _sat , and R ₄ are defined as in (1).
(7) In equation (2),
A is a group of the formula (1a) WN = N-Ar- or (1c) Ar-N (R ₄ ) -N = CH-W-
V is, - (CH _{2) 2} - and is,
p is 1,
q is 0,
X ₁ , X ₂ , C _sat , C ′ _sat , and R ₄ are defined as (1)
The compound according to any one of (1) to (5), wherein W is defined as (2).
(8) Formula

[Where
A is a group of the formula (1a) WN = N-Ar- or (1b) Ar-N = NW-
Y ₁ is a divalent group selected from phenylene, cyclohexylene, and C ₁ -C ₃ alkylene;
W is a fused or non-fused aromatic or non-aromatic heterocycle containing quaternary ammonium;
Ar is defined as (2)]
The compound according to any one of (1) to (4), which corresponds to the compound of
(9) Formula

[Where
A is a group of the formula (1a) WN = N-Ar- or (1b) Ar-N = NW-
R ₄ is methyl or tert-butyl;
W is a fused or non-fused aromatic or non-aromatic heterocycle containing quaternary ammonium;
X ₁ and C _sat are defined as (1)
W and Ar are defined as (2)]
The compound according to any one of (1) to (5), which corresponds to the compound of
(10) A is the formula

The compound according to (8) or (9), which is a group of
(11) A method for dyeing human keratin fibers, comprising a suitable cosmetic medium containing at least one disulfide dye selected from the dyes of formula (1) or (2) according to (1) Applying an object to said fibers.
(12) The method according to (11), wherein the staining composition further comprises at least one reducing agent.
(13) The method according to (11) or (12), comprising a step of pretreating keratin fibers with at least one reducing agent before applying the dyeing composition.
(14) The method according to any one of (11) to (13), further comprising a step of treating the keratin fibers with at least one reducing agent (post treatment) after applying the dyeing composition.
(15) The method according to (14), wherein the at least one reducing agent is selected from thiol, phosphine, bisulfite, and sulfite.
(16) The method according to (15), wherein the at least one reducing agent is selected from thioglycolic acid, cysteine, homocysteine, thiolactic acid, and salts of these thiols.
(17) The method according to (16), wherein the at least one reducing agent is selected from thiol, phosphine, bisulfite, and sulfite.
(18) The method according to (17), wherein the at least one reducing agent is selected from thioglycolic acid, cysteine, homocysteine, thiolactic acid, and salts of these thiols.
(19) The method according to any one of (11) to (18), wherein the staining composition further comprises at least one oxidizing agent.
(20) The method according to any one of (11) to (19), comprising a step of post-treating keratin fibers with at least one oxidizing agent.
(21) Any of (11) to (20), comprising post-treating keratin fibers with at least one modifier, and optionally also post-treating keratin fibers with at least one oxidizing agent The method described in 1.
(22) The method according to (21), wherein the oxidizing agent is selected from hydrogen peroxide, urea peroxide, alkali metal bromate, peracid group salt, and enzyme.
(23) at least one disulfide dye of formula (1) or (2) is present in the dyeing composition in an amount ranging from 0.001 to 50% by weight relative to the total weight of the composition, from (11) (22) The method according to any one of (22).
(24) A dyeing composition comprising in a suitable cosmetic medium at least one disulfide dye selected from the dyes of formulas (1) and (2).

Claims (9)

Formula (3)

[Where
A is a group of the formula (1a) WN = N-Ar- or (1b) Ar-N = NW-
Y ₁ is a divalent group selected from phenylene, cyclohexylene, and C ₁ -C ₃ alkylene;
W is the formula

[Z ₁ , Z ₂ , Z ₃ , Z ₄ , and Z ₅ are each independently N or —CH═,
R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ , R ₁₉ , and R ₂₉ are independently of one another, hydrogen, halogen, or saturated or unsaturated, linear or branched, a C ₁ -C ₁₄ alkyl,
An is an anion]
Selected from the cationic rings of
Ar is unsubstituted or at least one halogen atom, at least one alkyl group, at least one hydroxyl group, at least one alkoxy group, at least one hydroxyalkyl group, or at least one amino group or (di- A C ₅ or C ₆ aryl group substituted with an alkylamino group and a naphthyl-type aromatic bicycle ]
Compound. A is the formula

Is a group A compound according to claim 1. A method for dyeing human keratin fibers, wherein a dye composition comprising at least one disulfide dye selected from the dyes of formula (3) according to claim 1 in a suitable cosmetic medium is applied to the fibers. A method comprising the steps of: 4. The method of claim 3 , wherein the staining composition further comprises at least one reducing agent. 5. A method according to claim 3 or 4 , comprising pre-treating the keratin fibers with at least one reducing agent prior to applying the dyeing composition. 6. The method according to any one of claims 3 to 5 , comprising a step (post-treatment) of treating keratin fibers with at least one reducing agent after applying the dyeing composition. The method according to any one of claims 3 to 6 , wherein the staining composition further comprises at least one oxidizing agent. Equation (3) at least one disulfide dyes, present in the dyeing composition in an amount ranging from 0.001 to 50% by weight relative to the total weight of the composition, according to any of claims 3 to 7 Method. A dyeing composition comprising in a suitable cosmetic medium at least one disulfide dye selected from the dyes of formula (3) according to claim 1 .